CN110372902A - A kind of fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic - Google Patents
A kind of fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic Download PDFInfo
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- CN110372902A CN110372902A CN201910678863.7A CN201910678863A CN110372902A CN 110372902 A CN110372902 A CN 110372902A CN 201910678863 A CN201910678863 A CN 201910678863A CN 110372902 A CN110372902 A CN 110372902A
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- fluorine
- quaternary ammonium
- side chain
- ammonium salt
- anion
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 50
- 239000011737 fluorine Substances 0.000 title claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920002098 polyfluorene Polymers 0.000 title claims abstract description 48
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 35
- -1 ether compound Chemical class 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 7
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 claims description 3
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 4
- 229940006460 bromide ion Drugs 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 25
- 229920000090 poly(aryl ether) Polymers 0.000 description 18
- 229930185605 Bisphenol Natural products 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 150000002500 ions Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 108010021119 Trichosanthin Proteins 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Electrochemistry (AREA)
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- Polymers & Plastics (AREA)
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- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Fuel Cell (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of fluorine-containing polyfluorene ether anion-exchange membranes of side chain bi-quaternary ammonium salt ionic.Fluorine-containing polyfluorene ether compound containing dimethylamine sidechains and bromoalkane quaternary ammonium compounds are obtained the fluorine-containing polyfluorene ether compound of side chain bi-quaternary ammonium salt ionic by single step reaction by the present invention, and anion-exchange membrane then is made by solution casting method.The anion-exchange membrane has excellent mechanical property and thermal stability, and bromide ion conductivity is significantly improved than the fluorine-containing polyfluorene ether anion-exchange membrane of the side chain containing mono-quaternaries.
Description
Technical field
The present invention relates to a kind of fluorine-containing polyfluorene ether anion-exchange membranes of side chain bi-quaternary ammonium salt ionic, belong to amberplex
Material Field.
Background technique
Anion-exchange membrane is that containing positively charged group there is selection to penetrate anions in a kind of chemical structure
The thin polymer film of function is widely used in electrodialysis, diffusion dialysis, water electrolysis, all-vanadium flow battery, alkaline fuel cell etc.
Field.Due to high resistant vanadium performance, the features such as low fuel permeability, anion-exchange membrane is in all-vanadium flow battery and alkalinity combustion
Expect that there is very big application potential in battery, the research and development and performance optimization of novel anionic exchange membrane material are also constantly subjected to science
The concern on boundary and industry.However, the generally existing low conductivity of anion-exchange membrane currently on the market, stability difference etc. are asked
Topic, it is difficult to realize the application of large-scale commercial.
Traditional quaternary anion-exchange membrane mainly passes through the particular functional on quaternizing agent and polymer backbone
Group's reaction introduces cation group and is prepared.For example, Meng Yuezhong et al. (Chinese invention patent CN102516526B and document
Int. J. Hydrogen Energy, 2012,37,16168-16176) disclose a kind of poly- containing quaternary ammonium salt side and fluorenyl
Aryl oxide anion-exchange membrane, chloride conductance rate is 3.3 mS cm-1 at room temperature, and has enough mechanical strengths, energy
Enough meet the application demand of alkaline fuel cell and all-vanadium flow battery.Such method is drawn cation group by single step reaction
The specific position for entering polymer backbone prepares anion-exchange membrane, simple process, and reaction condition is mild.However, yin obtained
The cation group of amberplex directs or through shorter aliphatic chain and is connected on main chain, and ion-mobility is lower, no
Conducive to the aggregation of quaternary ammonium salt ion, effective anion transmission channel is formed, improves anionic conduction rate.Further, since ion
Group is closer apart from polymer backbone, reduces the chemical stability of film to a certain extent.
Therefore, by introducing double quaternary ammonium ion flexible side-chains on fluorine-containing polyfluorene ether, side chain bi-quaternary ammonium salt ionic is synthesized
Fluorine-containing polyfluorene ether anion-exchange membrane is conducive to the activity and aggregation extent that improve cation group in amberplex, with
The anion-exchange membrane with outstanding ion transmission performance and chemical stability is obtained, anion-exchange membrane investigation of materials is sent out
Exhibition has great importance.
Summary of the invention
The purpose of the invention is to overcome the deficiencies in the prior art, by introducing double quaternary ammonium ions on fluorine-containing polyfluorene ether
Flexible side-chains synthesize a kind of fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic.The side chain bi-quaternary ammonium salt from
The fluorine-containing polyfluorene ether anion-exchange membrane of subtype has simple process, ionic conductivity height, good mechanical property, chemical stability height etc.
Advantage has important application prospect in amberplex field.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic, by following structural formula side chain bi-quaternary ammonium salt from
The fluorine-containing polyfluorene ether compound composition of subtype:
X is any anion in formula, and it be 10 ~ 400, y is 1 ~ 4 that m, which is 1 ~ 400, n,.
The preparation method of the fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic, specifically includes the following steps:
(1) it prepares the fluorine-containing polyfluorene ether compound of side chain bi-quaternary ammonium salt ionic: the fluorine-containing polyfluorene containing dimethylamine sidechains is etherified
Conjunction object, which is dissolved in polar non-solute, is configured to solution A；Then, by 0.5 ~ 1.5 times of mole of above-mentioned dimethylamine group
Bromoalkane quaternary ammonium compounds Br-y-QA, which is dissolved in polar non-solute, is configured to solution B；Then, by solution B in argon
It is slowly dropped in solution A under the protection of gas, continues to stir 10 ~ 50 h at 20 ~ 80 DEG C after completion of dropwise addition；Finally, will reaction
Object is fitted into dialysis bag, in deionized water dialysis 3 ~ 10 days, and drying 10 ~ 40 hours is removed water at 80 ~ 120 DEG C, obtains side
The fluorine-containing polyfluorene ether compound of chain bi-quaternary ammonium salt ionic；
(2) it prepares anion-exchange membrane: the fluorine-containing polyfluorene ether compound of step (1) the side chain bi-quaternary ammonium salt ionic is dissolved in
It is configured to the solution of 1 ~ 8 wt.% in polar non-solute, then casts on horizontal positioned glass plate, in 40 ~ 100 DEG C
A conventional oven in dry 10 ~ 50 hours, in 60 ~ 150 DEG C of vacuum drying oven dry 10 ~ 50 hours to get side chain double seasons
The fluorine-containing polyfluorene ether anion-exchange membrane of Ammonium Salt Ionic type.
The chemical structure of fluorine-containing polyfluorene ether compound containing dimethylamine sidechains described in step (1) is as follows:
It is 10 ~ 400 that m, which is 1 ~ 400, n, in formula；
The chemical structure of the bromoalkane quaternary ammonium compounds Br-y-QA is as follows:
Y is 1 ~ 4 in formula.
The concentration of solution A is 1 ~ 10 wt.% in step (1), and the concentration of solution B is 5 ~ 10 wt.%.
It is 1 ~ 5 mL/min that solution B, which is added drop-wise to the speed in solution A, in step (1).
Prepared anion-exchange membrane is in step (2) with a thickness of 40 ~ 80 μm.It is above in order to preferably realize the present invention
Polar non-solute in the step includesN,NDimethyl acetamide,N,NDimethylformamide,NCrassitude
Ketone, dimethyl sulfoxide, any one in 1,3- dimethyl-2-imidazolinone.
The obtained fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic of the present invention can be used as battery diaphragm
Material.
Preparation method of the present invention be preferred embodiment, the predictable reasonable temperature of one of skill in the art, when
Between and other reaction conditions be invention which is intended to be protected, it is not limited to above-mentioned reaction condition.
Fluorine-containing polyfluorene ether compound containing dimethylamine sidechains and bromoalkane quaternary ammonium compounds are passed through one by the present invention
Step reaction obtains the fluorine-containing polyfluorene ether compound of side chain bi-quaternary ammonium salt ionic, and anion exchange then is made by solution casting method
Film.
Compared with prior art, the present invention has the effect that
(1) raw material that the present invention uses is cheap for common industrial chemicals, is easy to get；
(2) present invention introduces quaternary ammonium salt group with reacting for bromine group by dimethylamine group, and reaction condition is mild, and passes through
Adjust the ion exchange capacity that the content of dimethylamine group in polymer is controllably film-made.
(3) present invention is conducive to pendant cationic base using flexible bis-quaternary ammonium salt cationic side chain and fluorine-containing aromatic main chain
Group mutually assembles in film forming procedure, mutually separates with main chain formation, to form ion transmission channel, therefore gained anion is handed over
It changes film while there is excellent bromide ion conductivity and oxidation stability.
Detailed description of the invention
Fig. 1 is the side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE- prepared in the embodiment of the present invention 4
The nuclear magnetic resonance spectroscopy of 40-C3.
Fig. 2 is the side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE- prepared in the embodiment of the present invention 4
The infrared spectroscopy of 40-C3.
Fig. 3 is the side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE- prepared in the embodiment of the present invention 6
The nuclear magnetic resonance spectroscopy of 40-C6.
Fig. 4 is the side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE- prepared in the embodiment of the present invention 6
The infrared spectroscopy of 40-C6.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
The preparation of the fluorine-containing polyfluorene ether compound PFE-40 of embodiment 1
Method in fluorine-containing polyfluorene ether compound PFE-40 reference literature prepare (Int. J. Hydrogen Energy, 2012,
37,16168-16176).By the 0.7434 g(1.6 mmol of fluorenyl bis-phenol DABPF containing dimethylamine group), bisphenol fluorene
0.8410 g(2.4 mmol) and 1.3500 g of decafluorobiphenyl (4.04 mmol) be dissolved in 12 mLN-In methyl pyrrolidone,
Add 1.2g(8mmol) cesium fluoride and 0.5 g(12 mmol) calcium hydride, then reacts in the protection of argon gas at room temperature
24 h.After reaction, product is poured into be precipitated in 500 mL deionized waters and is precipitated, be re-dissolved in two after precipitating is collected by filtration
It in chloromethanes, is subsequently poured into methanol and precipitating is precipitated, precipitating is collected by filtration, dry 24 hours at 80 DEG C of vacuum drying oven to get arriving
Fluorine-containing polyfluorene ether compound PEF-40.Yield: 98%.
The preparation of the fluorine-containing polyfluorene ether compound PFE-20 of embodiment 2
Experimental procedure is same as Example 1, unlike the fluorenyl bis-phenol DABPF containing dimethylamine group and bisphenol fluorene feed intake
Amount.In the present embodiment, the inventory of the fluorenyl bis-phenol DABPF containing dimethylamine group is 0.3717 g(0.80 mmol), bis-phenol
The inventory of fluorenes is 1.1213 g(3.2 mmol).Reaction obtains fluorine-containing polyfluorene ether compound PFE-20.Yield: 97%.
The preparation of 3 side chain mono-quaternaries ionic polyarylether containing fluorene compound Q A-PFE-40 of embodiment
Synthesis (Int. J. in side chain mono-quaternaries ion polyarylether containing fluorene compound Q A-PFE-40 reference literature
Hydrogen Energy, 2012,37,16168-16176).It will be obtained fluorine-containing in 1.00 g(1.16 mmol) embodiment 1
Polyfluorene ether compound PFE-40 is dissolved in 20 mLN-The solution of 5 wt.% is made in methyl pyrrolidone, then slowly to anti-
Answer and 0.1 mL(1.8 mmol be added dropwise in system) iodomethane, after completion of dropwise addition, reaction be protected from light at room temperature under protection of argon gas into
20 h of row.After reaction, product is poured into be precipitated in 200 mL deionized waters and is precipitated, precipitating is then collected by filtration, uses third
Ketone cleans 3 ~ 5 times, and 12 h are dried in vacuo at 80 DEG C, obtain side chain mono-quaternaries ion polyarylether containing fluorene compound Q A-PFE-
40。
The preparation of 4 side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE-40-C3 of embodiment
Fluorine-containing polyfluorene ether compound PFE-40 obtained in 1.00 g(1.16 mmol) embodiment 1 is dissolved in 20 mLN-
It is made the solution of 5 wt.% in methyl pyrrolidone, while by 0.45 g(1.74 of bromoalkane quaternary ammonium compounds Br-1-QA
Mmol) it is dissolved in 4.5 mLN-The solution of 10 wt%, bromoalkane quaternary ammonium compounds Br-1-QA ginseng is made in methyl pyrrolidone
It prepares according to the method in document (J. Mater. Chem. A, 2016,4,13938-13948).Then, in the protection of argon gas
It is lower that bromoalkane quaternary ammonium compounds solution is slowly added dropwise in fluorine-containing polyfluorene ethereal solution by the speed of 5 mL/min, knot is added dropwise
Shu Hou, in 40 DEG C of 40 h of reaction under the protection of argon gas.After reaction, product is fitted into dialysis bag, in deionized water
Dialysis 5 days, deionized water twice was during which replaced daily.Then by product at 80 DEG C forced air drying 12 hours, then at 80 DEG C
Vacuum drying 12 hours, obtains the fluorine-containing polyfluorene ether compound DQA-PFE-40-C3 of side chain bi-quaternary ammonium salt ionic；Yield: 96%.
The data of the nuclear magnetic resonance spectroscopy of the compound are as follows:1H NMR (400 MHz, DMSO-d6) δ 7.94 (s, 1H),
7.44 (d, 2H), 7.27 (d, 1H), 7.06 (d, 2H), 6.96 (s, 1H), 4.75 (s, 1H), 3.15
(m, 1H), 3.04 (t, 1H), 2.20 (s, 1H) infrared datas are as follows: FT-IR (cm-1) υ 3413,3039,2923,
2850, 1647, 1599, 1487, 1240, 1207, 1171, 1070, 982, 816, 729.The side chain being prepared
The nuclear magnetic resonance spectroscopy of bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE-40-C3 is shown in Fig. 1, and infrared spectrogram is shown in figure
2。
The preparation of 5 side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE-20-C3 of embodiment
Experimental procedure is same as Example 4, the difference is that fluorine-containing polyfluorene ether raw material PFE-40 uses the fluorine-containing polyfluorene in embodiment 2 instead
Ether compound PFE-20, inventory are 1.55 g(2.32 mmol).Reaction obtains side chain bi-quaternary ammonium salt ionic polyarylether
Close object DQA-PFE-20-C3.Yield: 98%.
The preparation of 6 side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE-40-C6 of embodiment
Experimental procedure is same as Example 4, the difference is that bromoalkane quaternary ammonium compounds raw material uses Br-4-QA instead, feeds intake
Amount is 0.53 g(1.74 mmol).Reaction obtains side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE-40-
C6.Yield: 96%.The data of the nuclear magnetic resonance spectroscopy of the compound are as follows:1H NMR (400 MHz, DMSO-d6) δ 7.95
(s, 1H), 7.42 (d, 2H),7.34(s, 2H), 7.14 (s, 1H), 4.71 (d, 1H), 3.09 (s, 2H),
1.71 (d, 1H), 1.33 (s, 1H).Infrared data are as follows: FT-IR (cm-1) υ 3413,3066,3037,2927,
2862, 2819, 2757, 1649, 1602, 1487, 1205, 1170, 1070, 981, 816, 746, 729.Preparation
The hydrogen nuclear magnetic resonance spectrogram of obtained side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE-40-C6 is shown in Fig. 3, red
External spectrum figure is shown in Fig. 4.
The preparation of 7 side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE-20-C6 of embodiment
Experimental procedure is same as Example 4, unlike raw material use 1.00 g(1.50 mmol instead) it is fluorine-containing poly- in embodiment 2
Fluorenes ether compound PFE-20 and 0.68 g(2.25 mmol of bromoalkane quaternary ammonium compounds Br-4-QA).Reaction is contained
20 mol% long side chain bi-quaternary ammonium salt ionic polyarylether containing fluorene compound DQA-PFE-20-C6.Yield: 97%.
Embodiment 8 is based on above-mentioned quaternary ammonium salt ionic polyarylether containing fluorene compound and prepares anion-exchange membrane
The above-mentioned side chain mono-quaternaries ionic of 0.5 g and the fluorine-containing polyfluorene ether compound of side chain bi-quaternary ammonium salt ionic are taken, is dissolved in
10 mL N-5 wt% solution are made in methyl pyrrolidone, then pours and casts from horizontal positioned plate glass, in constant temperature oven
In 80 DEG C drying 12 hours, then 80 DEG C drying 12 hours in vacuum drying oven, i.e., form membranaceous product in glass plate.By film from
It is peeled on glass plate, then impregnates in deionized water, target side chain mono-quaternaries ionic and side chain bi-quaternary ammonium salt is made
Ionic polyarylether containing fluorene anion-exchange membrane product.
9 side chain mono-quaternaries ionic of embodiment and the fluorine-containing polyfluorene ether anion exchange film properties of side chain double quaternary ammonium salt type
Test
Using titration test ion exchange capacity, bromide ion conductivity is tested using AC impedence method, using universal testing machine
Tensile property is tested, using (the VO of 1M2)2SO42 weeks test oxidation stabilities of solution soaking at room temperature.Through characterizing, side chain single cropping ammonium
The performance of salt ion type and the fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic is as shown in the table:
The performance of 1 side chain mono-quaternaries ionic of table and the fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic
The test data of table 1 shows that the anion-exchange membrane QA-PFE-40 compared to side chain mono-quaternaries ionic, side chain are double
Close, but the bromine of the ion exchange capacity of quaternary ammonium salt ionic anion-exchange membrane DQA-PFE-20-C3 and DQA-PFE-20-C6
Ionic conductivity significantly improves, it was demonstrated that distribution of the regulation ionic group in anion-exchange membrane has obvious beneficial effect.
DQA-PFE-40-C3 and DQA-PFE-40-C6 is due to having ion exchange capacity more higher than other samples, bromide ion conduction
Rate further increases.
Claims (7)
1. a kind of fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic, which is characterized in that by following structural formula
The fluorine-containing polyfluorene ether compound composition of side chain bi-quaternary ammonium salt ionic:
X is any anion in formula, and it be 10 ~ 400, y is 1 ~ 4 that m, which is 1 ~ 400, n,.
2. a kind of preparation side of the fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic as described in claim 1
Method, which is characterized in that specifically includes the following steps:
(1) it prepares the fluorine-containing polyfluorene ether compound of side chain bi-quaternary ammonium salt ionic: the fluorine-containing polyfluorene containing dimethylamine sidechains is etherified
Conjunction object, which is dissolved in polar non-solute, is configured to solution A；Then, by 0.5 ~ 1.5 times of mole of above-mentioned dimethylamine group
Bromoalkane quaternary ammonium compounds Br-y-QA, which is dissolved in polar non-solute, is configured to solution B；Then, by solution B in argon
It is slowly dropped in solution A under the protection of gas, continues to stir 10 ~ 50 h at 20 ~ 80 DEG C after completion of dropwise addition；Finally, will reaction
Object is fitted into dialysis bag, in deionized water dialysis 3 ~ 10 days, and drying 10 ~ 40 hours is removed water at 80 ~ 120 DEG C, obtains side
The fluorine-containing polyfluorene ether compound of chain bi-quaternary ammonium salt ionic；
(2) it prepares anion-exchange membrane: the fluorine-containing polyfluorene ether compound of step (1) the side chain bi-quaternary ammonium salt ionic is dissolved in
It is configured to the solution of 1 ~ 8 wt.% in polar non-solute, then casts on horizontal positioned glass plate, in 40 ~ 100 DEG C
A conventional oven in dry 10 ~ 50 hours, in 60 ~ 150 DEG C of vacuum drying oven dry 10 ~ 50 hours to get side chain double seasons
The fluorine-containing polyfluorene ether anion-exchange membrane of Ammonium Salt Ionic type.
3. preparation method according to claim 2, which is characterized in that step (1) is described to contain the fluorine-containing of dimethylamine sidechains
The chemical structure of polyfluorene ether compound is as follows:
It is 10 ~ 400 that m, which is 1 ~ 400, n, in formula；
The chemical structure of the bromoalkane quaternary ammonium compounds Br-y-QA is as follows:
Y is 1 ~ 4 in formula.
4. preparation method according to claim 2, which is characterized in that the concentration of solution A is 1 ~ 10 wt.% in step (1),
The concentration of solution B is 5 ~ 10 wt.%.
5. preparation method according to claim 2, which is characterized in that solution B is added drop-wise to the speed in solution A in step (1)
Degree is 1 ~ 5 mL/min.
6. preparation method according to claim 2, which is characterized in that prepared anion exchange film thickness in step (2)
Degree is 40 ~ 80 μm.
7. preparation method according to claim 2, which is characterized in that the polar non-solute includesN,NDiformazan
Yl acetamide,N,NDimethylformamide,NMethyl pyrrolidone, dimethyl sulfoxide, in 1,3- dimethyl-2-imidazolinone
Any one.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530511A (en) * | 2020-06-18 | 2020-08-14 | 福州大学 | Column [5] arene cross-linked fluorine-containing polyarylether anion exchange membrane and preparation method thereof |
| CN111662446A (en) * | 2020-06-17 | 2020-09-15 | 福州大学 | Fluorine-containing polyarylether anion exchange membrane with low surface resistivity and high oxidation stability and preparation method thereof |
| CN111871222A (en) * | 2020-07-16 | 2020-11-03 | 福州大学 | Preparation method of quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on pillared [5] arene |
| CN112563520A (en) * | 2020-10-27 | 2021-03-26 | 浙江大学 | Homogeneous catalyst and catalyst layer of anion exchange membrane fuel cell |
| CN114133555A (en) * | 2021-12-09 | 2022-03-04 | 福州大学 | Preparation method of cross-linked fluorine-containing polyfluorene ether anion exchange membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516526A (en) * | 2011-12-01 | 2012-06-27 | 中山大学 | Polyarylether compound containing quaternary ammonium salt side group and fluorenyl and preparation method and application thereof |
| CN106784946A (en) * | 2016-12-01 | 2017-05-31 | 长春工业大学 | Fuel cell polyfluorene ether nitrile cross-linking type anion exchange membrane material of cation group functionalization and preparation method thereof |
-
2019
- 2019-07-25 CN CN201910678863.7A patent/CN110372902B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516526A (en) * | 2011-12-01 | 2012-06-27 | 中山大学 | Polyarylether compound containing quaternary ammonium salt side group and fluorenyl and preparation method and application thereof |
| CN106784946A (en) * | 2016-12-01 | 2017-05-31 | 长春工业大学 | Fuel cell polyfluorene ether nitrile cross-linking type anion exchange membrane material of cation group functionalization and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| DONGYANG CHEN，ET AL.: "Synthesis and characterization of quaternary ammonium functionalized fluorene-containing cardo polymers for potential anion exchange membrane water electrolyzer applications", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| 贺玉彬: "微相分离阴离子交换膜结构设计与性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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|---|---|---|---|---|
| CN111662446A (en) * | 2020-06-17 | 2020-09-15 | 福州大学 | Fluorine-containing polyarylether anion exchange membrane with low surface resistivity and high oxidation stability and preparation method thereof |
| CN111530511A (en) * | 2020-06-18 | 2020-08-14 | 福州大学 | Column [5] arene cross-linked fluorine-containing polyarylether anion exchange membrane and preparation method thereof |
| CN111871222A (en) * | 2020-07-16 | 2020-11-03 | 福州大学 | Preparation method of quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on pillared [5] arene |
| CN112563520A (en) * | 2020-10-27 | 2021-03-26 | 浙江大学 | Homogeneous catalyst and catalyst layer of anion exchange membrane fuel cell |
| CN114133555A (en) * | 2021-12-09 | 2022-03-04 | 福州大学 | Preparation method of cross-linked fluorine-containing polyfluorene ether anion exchange membrane |
| CN114133555B (en) * | 2021-12-09 | 2023-05-16 | 福州大学 | Preparation method of cross-linked fluorine-containing polyfluorene ether anion exchange membrane |
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